Cellulose derivative compositions



.CELLULOSE DERIVATIVE COMPOSITIONS Arthur L. Alleweltj-West Chester, Pa.,- assignor to-Ameri- CflH'VlSCOSQ COI'PQl'fifiOIl, Philadelphia, Pa.,xacorpora- :tiunzofzDelaware N "Drawing. Original application April 1, 1952, 'Serial ?No. 279,922. Divided --and this application May "'8, 1953, Serial-No. 353,902

15 .Claims. (Cl. 260-47) "This invention relates to compositions comprising .thiourethanesof acyl esters of ,celluloseisuch as thioure- :thanes of cellulose acetate.and extruded and molded articles cornprising'them. 'This applicationis a division of my copending application Serial'No. 279;922,fiied Apr'il1i1,'1952.

'In the'thiourethanes of cellulose acyl esters ofthecompositions of the invention, some hydroxyl groups of'the cellulose molecule are replacedby acyl groups 0 e t-X .and fthiourethane groups s 13 -o t in which X represents an =alkyl 'radical containing "from 1 1 to 16 carbon atoms, R and "R" are eachselectedfrorn the'group consisting of hydrogen, a saturated or unsaturated aliphatic hydrocarbongroup containing from l to' 1-2 carbon atoms, an alicyclicradical 'havingratotal of not more than 12 carbon atoms and "comprising asingle' 4- to 6-membered carbocyclic ring, a heterocyclicxradicalhaving'. a total of not -more. than 12 carbon atoms and comprising a single 5- -to 6=membered'rin'g,=an aryl radical of "the benzene series, and an aryl-ra'dical oft-he benzene 1 series having aliphatiehydrocarbon groups containing a total o'f not more than six carbon atoms-attached*to=the benzene ring, R and =R' being'the same or different. "The vterm .cellulose when used 'herein includes celluloses having any average molecular weight or 'degree-ofpoly- *me'rizatiomsueh as a'DJP. of 50 to400 or more.

W-hiIethe ratios of the thiourethane and the acyl' groups to: the anhydroglucose units in the cellulose derivatives may vary; in the preferred" embodiment the-ratio of 'thiou- "rethane' groups to anhydroglucose unitsis' from-123 161510, most desirablyabout 1:3 to1z6, and the "ratio of acyl groups toranhydroglucose-units is from lz'l 'to' 1.75:1.

These esters may beobtained by the methods disclosed 55 in; my earlier application supraand the disclosure is incorporated herein byreference.

:The cellulose thiourethanes which are acylated maybe produced by any suitable: method. They may be obitained-"by' reacting arprimary: orsecondary amine-with:- a 'fxantho-fattyiacid. resulting 'from-the reaction of cellulose :xanthate-andra monohalogenated .fatty -:acid, :e. ;g.,' chloracetic acid. Preferably,.'however, thethiourethane' isobtained lby..;the processzdescribedinmy pending application .Serial:No. '65,7.42, ".filed. December 16, 1948, now I'Batent No.;2,705,231, issued -March29, 1955, and the'dis'closure thereof incorporated herein by reference. That process which'yields products which do not. contain free =carboxyl ,"igroups'tand. are 'therefere'. colorless or substantiallyvcolor- -.1ess, involvesi'reacting viscose with .aiwater-soluble zsalt'zof 12a: di-cort trievalent :metal, :e. :.-g., ilZlIlC :sulfate, int-aqueous thereof esolutionccontainingsodium sulfate, :to form arscomplex wliihis then..dispersed.in an aqueous solutionof a primary ,orsecondary amine to producethe cellulose thiourethane.

.Cellulosethiourethanes which may be acylated to pro- 5 .duce theresters (described herein include cellulose thiourefthane, .cellulose phenylthiourethane, cellulose ethylthiourethane, cellulose amylthiourethane, cellulose :monoand dil-benzyl,thiourethanes, cellulose allyland methallyl- ,thioure'thanes, cellulose cyclohexylthiourethane, cellulose 'dibutylthiourethane, cellulose dimethylthioureithane, cellulose pyridylthiourethane, etc.

The acid anhydrides which may be ,used in .acylating the-cellulose thiourethane are the .anhydrides of thejfat'ty acidscontaining'trom '2 M16 carbon atoms,i. e., acidsof 'the.aliphathic-series from andincluding acetic acid wand including ,stearic acid.

"These'new esters are colorless ,or essentially colorless powders which are variously solublein organic solvents, exhibitplasticproperties, and receptivity'forthe acid dye- 20 stuffs. They find important use in the plastic and coating -arts alone or as modifying components of plastic compositions.

"In general, the estershave softening temperatures between 200 and 1260 C. and exhibit good flow character- -'istics under pressure at temperatures between 170 C. and

210 .C. .Thus,with or without the addition of aplasticiz- "ing agentgtheesters maybe heated under pressure'to betweenl'lt'.) C. and "216C. and extruded by. means of :conventional extruding devices to form shaped articles. :For example, athiourethane of the cellulose ester or a mixtureof'thethiourethanesof cellulose esters may' be 'gplaced' in:a heatedcylinder. and when reduced to a melt --un',der pressure may be forced through a spinneretby means of'apiston, totorm filamentsorthreads. Or the ester may be fed into a screw mixer-extruder and extruded 'as7a translucentc'ylindrical rod which is broken intosmall "pieces andfe'd into "a. 'screw extruder from which it.is forcedthrough the'orifices'ofa spinneret or other shaping means,*to obtain'filaments,'filmsytapes, ribbons, tubes,

40 bands, etc. The-melt may'be extruded under, pressure onto asupporting-surfaceto form a pellicle which is. subsequently stripped off the support :or it maygbeextruded onto a substrate' towhich it is adhered'or anchored with "theaid 'of' pressure, thus producing a compositeproduct, ,for instance, composite-sheetma-terial.

{Also the" thiourethanes of' the-cellu1ose acyl esters may 4 be molded bycompression or injection molding techniques to obtain massive molded articles of any desired sizeiand cross-section.

Compositions comprising the'thiourethanes'of-thecellu- 'lose-acyl esters-may be formed by dissolving themin a 'suitable solvent and such compositions may 'be formed into filaments or threads'by-wetor 'dry spinning-methods, cast-to*'fi1rns,--or otherwise shaped with evaporation or 1 extraction-ofthe solvent. The solutions'may further be used as coating compositions, for laminating similar, and diss'imilar surfaces, as adhesives, etc.

-Many of the thiourethanes of the acyl-esters of cellulose which come within the scope of the invention-are soluble in :acetone, --dimethylformamide, and 'dimethylacetarnide,

or in at least one of the solvents mentioned. Solutions thereof in such=solvents maybe used.

FThethiourethanes of the esters may be merely swollen :or plasti'cizedby' thementioned solvents to obtain'plas'tic,

-rea'di'ly workableimasses.

Since-the 'thiourethanes of "the cellulose esters have "plastioor-flowcharacteristics under heating and: arecompatible with such plastic materials as cellulose acetate andrresins, 'of which' -the thermoplastic resins are particul larly-suitable,- theysmay be blended withthose base mate- =:rials- :in varying-amounts depending upon "thelimits of compatibility of the ester of the cellulose thiourethane ester may be added to a solution of cellulose acetate in v one of the mentioned solvents and spun into filaments having essentially the properties of normal cellulose acetate filaments but distinguished therefrom by a capacity to accept the acid dyestuffs without the use of dyebaths containing large proportions of special assistants or swelling agents for the acetate.

The thiourethanes of cellulose acyl esters also may be mixed with natural and at least initially thermoplastic synthetic resins and extruded or molded by known methods.

The components of these compositions may be mixed in.-

solution and extruded or the dry finely divided ingredients may be mixed in a Banbury mixer or on milling rolls and dissolved in a solvent, the solution being then extruded. Or the dry, finely divided ingredients may be compounded with or Without preliminary shaping to convenient pellet form, and molded by injection or compression molding techniques.

In molding the thiourethanes of the acylated cellulose I or mixtures thereof with other plastic materials, various molding adjuvants may be introduced into the moldingcomposition and in the case of mixtures of the thiourethanes of the esters and other plastic moldable substances the adjuvants, which may be fillers, plasticizing agents, dyes, pigments, mold lubricants, special effect materials such as metallic particles, etc., may be mixediwith' either of the primary components before they are mixed together or conjointly with compounding thereof. As

' fillers there may be used alpha-cellulose, wood flour, walnut shell flour, asbestos in the form of a powder or long or short fibers, finely divided silicon carbide, carbon black,

diatomaceous earth, slate dust, powdered rutile, powdered or flake mica, powdered quartz, fibers or cloth cuttings (e. g., fibers or cuttings of silk, rayon, wool, linen, cotton, nylon, glass fibers or cuttings of cloth made therefrom,

fibers of polymeric or copolymeric acrylonitrile or cloth made therefrom), ground cork, sand, etc.

As plasticizers there may be used phthalic acid esters including dimethyl, diethyl, dimethyl glycol, diethyl glycol, dibutyl glycol and dioctyl phthalates, triethyl citrate, cresyl glyceryl diacetate, triacetin, etc.

As mold lubricant there may be used zinc stearate, calcium stearate, mixtures thereof and natural and synthetic waxes.

Many thermoplastic resins may be modified by admixture with the acyl esters of the cellulose thiourethanes, including the polyamides such as nylon and polyesters particularly polymethylene terephthalates, and the synthetic thermoplastic resins obtained by the polymerization or interpolymerization of one or more polymerizable unsaturated monomers containing monoethylenic unsaturation. Examples of these resins are polystyrene, polyethylene, polymethylmethacrylate, polyvinyl chloride, polyvinylidene chloride, copolymers of vinyl chloride and vinyl acetate, and copolymers of vinyl chloride and vinylidene chloride (e. g., the product available commercially under the' trade name Saran) A specific preferred group of synthetic resins for admixture with the thiourethanes of the acyl esters of cellulose are those acrylonitrile polymers containing, in the polymer molecule, at least by weight of acrylonitrile.

The polymer may be the homopolymer polyacrylonitrile or a copolymer resulting from the copolymerization or interpolymerization of acrylonitrile with one or more other monoethylenically unsaturated monomers copolymerizable with acrylonitrile those copolymers which are of thermoplastic character being especially valuable for molding purposes.

Monomers which may be copolymerized with acrylonitrile to produce binary or ternary copolymers to be mixed with the thiourethanes of the cellulose acyl esters include: acrylic, alpha-chloracrylic and methacrylic acids; methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, 2-nitro-2-methylpropyl methacrylate, methoxymethyl methacrylate, beta-chlorethyl methacrylate and the corresponding esters of acrylic acid and alpha-chloracrylic acids; vinyl chloride, vinyl fluoride, vinyl bromide; vinylidene chloride, 1-chloro-1-bromo ethylene, vinylidene bromide, l-fluoro-l-chlorethylene, 1,1-difluoroethylene; methacrylonitrile, alpha-chloracrylonitrile; acrylamide, methacrylamide, N,N-dimethylacrylamide, alpha-chloracrylamide, or monoalkyl substitution products thereof; methyl vinyl ketone and methyl isopropyl ketone; vinyl carboxylates such as vinyl acetate, vinyl chloracetate, vinyl propionate and vinyl stearate; N-vinylimides such as N-vinyl phthalimide and N-vinylsuccinimide, methylenemalonic esters; itaconic acid anditaconic esters; trifluorochlorethylene; N-vinyl carbazole and vinyl-substituted heterocyclic amines such as the vinylpyridines including those having hydrocarbon groups containing a total of not more than four carbon atoms attached to the pyridine nucleus, e. g., 2-vinylpyridine, 2- methyl-S-vinylpyridine, vinylimidazoles, e. g., 1-viny1imidazole, N-vinylimidazole, 1-vinyl-2methylimidazole, etc.; vinyl furane; butyl vinyl sulfone, ethyl vinyl sulfone; ethylene, propylene, isobutylene, butene-l and butene-2; alkyl vinyl ethers; vinyl-sulfonic acid; ethylene-alpha, betadicarboxylic acids or their anhydrides or derivatives such as diethyl fumarate, diethyl maleate, diethyl citraconate, diethyl mesaconate; styrene, vinyl-naphthalene, and the like.

The thiourethanes of the acylated cellulose are particularly advantageous as blending or modifying agents for polyacrylonitrile and copolymers thereof which, of themselves, exhibit little or no recepticity for the acid dyes. Blends of those acrylonitrile polymers with the thiourethanes of the cellulose esters can be extruded or molded to obtain shaped articles which are receptive to the acid dyes and can be dyed to satisfactory shades under usual wool-dyeing conditions.

While the proportion of acrylonitrile in the polymer molecule is at least 50% by weight, it is frequently much higher depending on the ultimate use of the blend comprising the polymer. If the blend is to be spun from a solution to form filaments or threads, the copolymer should contain at least by weight of acrylonitrile in the polymer molecule, and not in excess of 20% by weight of the other monomer or monomers. Binarycopolymers containing by weight in the polymer molecule, from to 99% acrylonitrile and 1% to 15% of another monomer such as mentioned above, and ternary polymers containing, by weight in the polymer molecule, at least 80% acrylonitrile and from 1 to 19% each of two of the other monomers which are copolymerizable with acrylonitrile, and in which the three components total 100%, are preferred for fiber-forming purposes.

The acrylonitrile polymers high in polymerized acrylonitrile including polyacrylonitrile itself are soluble in such organic solvents as dimethylformamide and dimethylacetamide. Since those solvents also dissolve the thicurethanes of the cellulose esters, notably the phenyl thiourethane of acetyl cellulose, they may be used in preparing spinning and casting solutions of the mixture of polymer and cellulose ester thiourethane.

Acrylonitrile polymers containing less than 80% by weight of acrylonitrile in the polymer molecule are generally soluble in common solvents which do not dissolve the polymers containing the higher proportions of polymerized acrylonitrile. or example, they are generally soluble in acetone which is also a solvent for many of the new thiourethanes of acyl esters of cellulose. Mixtures ofthe polymers containing less than 80%, but not less than 50%, by weight of polymerized acrylonitrile "with -a-thiourethane =.of I an acyl-resten of rcellulose :tas'tde- -.-scribed herein, .for :example, .-a :phenylthiourethane :of

r acetylcellulose: may be dissolved in acetone and castzinto -films, applied as-coatings, and.-so.forth.

:The molecular weight of the thermoplasticzresinsmixed with the thiourethane of the cellulose-f-may varyrather widely, depending on the use to which the mixture is to be put. Preferably, 'the'resin has a molecular weight .of at least 5,000, but when the-composition comprises a vmixture of a thiourethane'of acyl cellulose and .--a polymeric material containing at least 80% polymerized acrylonitrile which is to be formed into filaments or; yarns, higher molecular weights are desirable and the :acrylonitrilepolymers may have a molecular weight up to"2'50,- OOO'or even higher.

The. following examples, in which the parts given are by'weight unless otherwise specified illustratespecific embodiments of .the invention. TheRoc'kwellhardness 'valueig'iven. in.'sorne of. the examples was measured on the "well-known Rockwell hardness tester.

Example 1 Fiftyparts of an allyl thioure'thane-o'f cellulose-containing one allyl =thiourethane *group per three anhy- -'droglucose"units were 'pretreatedwith 465 parts-of glacial I acetic acid -at"25 C. for 24 hours. The 'mixture was then placedxin a mixing Pfleiderer andcliilled to CMWllIh-COHtlDUOUS mixing. An acetylating mixture of '202 parts of 98% acetic anhy'drideand 2.64 parts 'of 955% sulfuric'acid, chilled to between "5 and 10 C., was added to the acid-swollen cellulose allylthiourethane 'in incrementsover a period of 10 minutes. ":The reac- Acetyl Calculated asPer- Ripening Time (hours) at =50 e.

; 1 cent-Acetic Acid "Example 2 Ten parts of the ester "obtained by ripening the acetyletion product of Example 1 for 288 hours at 50 C.-were mixed-with 90 parts of polystyrene. The-mixture was placed in a cylindrical compression mold having -a diameter of 1.25 inches. The mold was placed in'ahydraulic *press, heated by band heaters -to200' C.,"andthen subjected to a pressure of 4000 lbs/Sqfliri'ch for 2=minutes. *A translucent'rod'was obtained.

A standardized dyebath was preparedbydissolving' 5% of Glaubers salt, 3% of sulfuric acid (96% )"and 2% of the acid dye WoolFast Scarlet G. Supra (CI I.'No.' "252) (the percentages being on the weight of the article 'to'be dyed) in water. The melded rod was'entered into the bath at 55 C., the bath was brought to the boil-in 10 minutes, and boiled for minutes. The'rodwas dyed to agood red-shade. "in another'run, dioctylfphthalate was' added to thezblend of-tpolysty.rene.aand celluloseester allylthio'urethane, Lmakin'g :possible :a somewhat lower moldingtemperature.

" C. "for 264' hours.

-spinning procedure. a deep'fast shade in a "bath jprepare'das "described in About "7852 parts .of a cellulose -.-.phenylthiourethane containing one phenylthioure'thane ,group per three .anhy'dro'glucose units were .place'dlin .a.vessel..e quippe.d with mixing blades, "392 parts of acetic acidat SO" C. wereadd- .e'd, and 'the mixture was agitated for one .hour at 180 C. The temperature was 'thenre'ducedrto 16" LC. and

anacetylating medium chilled to 10 C. and consisting of #31'4I08 parts .of. acetic anhydride and "3.92 parts .of 100% sulfuric acid was added slowly until 'the temperature began to rise abovel20 .C. Addition of'the acetylating mixture was stoppeduntilthe risein temperature of the reaction mixture subsided. The remainder ffthe .acetylating medium was then added and'the reaction was allowed to proceed for two hours at between"33C. and 35 C., after which a mixture of 76.2 parts ofiwavter, 76.2 parts of glacial acetic acid and "4.18 .partsof iotmd to.contain.between .24.59.:.and..25.-56% combined of substitution of 1.4. to .1145 .acetyL.groups..per...anhydro glucose .unit. The .precipitatedproducts were -'.filtere'd, .washed. free of. acid, anddried atf60 .C...-forl24..hours.

acetic acid respectively, which correspond .to.a..degree These ,products were..soluble..in acetone, fdimethylformamide and .dimethylacetamide.

"Example From 10 to 30%. of theacetylestersof.cellulosephcnylthiourethane of Example 3 were. added:todiiferentlbatches of commercial cellulose acetate spinning -:.dop.e .using acetone as the solvent. The mixtures were dry-spun in accordance with the conventional cellulose acetate dry .Thefibers obtained were dyed to Example 2.

Example 5 Ten. parts ofa'phenylthiourethane-.of cellulose containing one phenylthiourethane group per threeranhydroglucose units were stirred with 90 parts .of glacialacetic acidat 25 C- for .1-6 8.hours. The product was .filtered and washed free of .acidwith wateruatroom temperature. The mass was continuously stirred during the-washing, and filtered betweeneachwashing. The purified product contained 4.06% combined acetic acid. It was soluble in 'dimethylformamide :and- :climethylacetamide,

insoluble in::acetone. I n

Example 6 as in Example 2.

:Examplei7 A mixture of 67.1jparts of anethyl'thiourethane of cellulose containing one ethylthiourethane-group per.3;" anhydroglucose units and.662.9 parts of water was'extra'cted with glacial acetic acid until all the water was replaced by -the =acetic.acid. The mass was dried. in a Vacuumidessiccator' over phosphorus.pentoxidez'fon l'8.hours..-afiter which the mixture. of 67. 1 parts cellulose' ethylthiourethane. and .633 parts-glacial .aceticaacid was placed in a-vessel equipped with-mixing blades and chilled'to 15 C.-with. continuous water mixtures.

. Example 2.

7 mixing. An acetylating medium chilled to about C. and consisting of 268 parts of acetic anhydride and 335 parts of 100% sulfuric acid was added to the mixing vessel until the reaction temperature began to rise rapidly. After the rise in temperature had subsided, the remainder of the acetylating medium was added and the reaction was continued for one hour at 33 C. A mixture of 174.5 parts of water, 174.5 parts of glacial acetic acid and 3.35 parts of 100% sulfuric acid was added. The reaction temperature rose to 45 C., then fell to 25 C. The acetylated lm'ixture was removed from the mixing vessel and stored in 'a glass container at 50 C. for ripening. Part of the mass was removed from the container after 48 hours. The ester Was precipitated as a white powder. It contained 41.38% combined acetic acid and was soluble in dimethylformamide, dimethylacetamide and acetone.

The remaining portion of the acetylation mixture was ripened-for 168 hours, after which the ester was precipitated as a white powder. It contained 27.9% combined acetic acid and was soluble in dimethylformamide and dimethylacetamide but insoluble in acetone and acetone- Mixtures comprising 10% of this ester and 90% polystyrene were molded as in Example 2. Rods so obtained were dyed to a satisfactory shade as in Example 2.

Example 8 A dimethylthiourethane of cellulose having a degree of substitution of one dimethylthiourethane group per 2.6

anhydroglucose units Was acetylated as in Example 3. The acidic esterification mixture was aged at 50 C. An acetyl ester, which contained 39.65% of combined acetic acid was precipitated in the form of a white powder from a portion of the mixture removed after the ripening had proceeded for 96 hours. 300 hours contained 24.7% combined acetic acid.

Rods obtained by molding these esters and mixtures thereof with polystyrene containing from 10 to 25% of the ester, under the conditions of Example 2, were dyed satisfactorily in a dyebath as described in Example 2.

Example 9 A solution was prepared by dissolving a blend of 12 parts of the longest ripened phenylthiourethane of secondary acetyl cellulose of Example 3 with 88 parts of a copolymer of 97% acrylonitrile and 3% vinyl acetate in 567 parts of dimethylacetamide, to obtain a solution of the blend. The solution was cast onto a heated surface to obtain a film.

The film dyed to a deeper shade in a dyebath as in Example 2 than control films of the acrylonitrile-vinyl acetate copolymer.

Example 10 A solution of the blend as in Example 9 was extruded through a slit in an extruding device into a setting bath comprising 60% dimethylacetamide and 40% water. The film was withdrawn from the bath, washed with water and dried. It dyed to a deeper shade in the standardized dyebath than a control film of the copolymer.

Example 11 A solution of the blend as in Example 9 was extruded through a slit in an extrusion device into isopropanol. The film thus formed was taken from the bath, washed with water and dried. It dyed to a deeper shade than a control film of the copolymer, in a bath prepared as described in Example 12 A blend of 88 -parts of a finely divided copolymer of 97% acrylonitrile and 3% of vinyl acetate with 12 parts of the phenylthiourethane of cellulose acetate of Example -5 was dissolved in 567 parts of dimethylacetamide. The 4 solution was c'astto' a film which Was dyed to a deeper The ester isolated after a ripening time of' shade of red in a dyebath as in Example 2 than a control film of the acrylonitrile-vinyl acetate copolymer. Similar films were obtained by extruding dimethylacetamide solu- Example 13 A blend of 88 parts of a copolymer of 97% acrylonitrile and 3% vinyl acetate with 12 parts of the longest ripened ethylthiourethane of acetyl cellulose of Example 7 was dissolved in 567 parts of dimethylacetamide. Films obtained from the solution were dyed to a deeper shade in a dyebath prepared as in Example 2 than a control film of the acrylonitrile-vinyl acetate copolymer.

. In all instances, the yarns, films and other shaped articles comprising a thiourethane of acylated cellulose in accordance with the invention was dyed to a deeper shade in the aqueous bath containing the acid dyestufi than the control article. Shaped articles comprising blends of the cellulose ester thiourethane and cellulose acetate were dyed satisfactorily in the absence of large amounts of special swelling agents or partial solvents for the cellulose acetate. The articles formed from blends of the cellulose ester thiourethanes and acrylonitrile polymers exhibited receptivity for the acid dyes even though, as in the case of the copolymer of acrylonitrile and vinyl acetate specifically exemplified herein, the polymer itself had no affinity for the acid dyes and the control film or other article was not colored or was merely tinted in the dyebath.

In preparing blends of the cellulose ester thiourethanes with organic acid esters of cellulose or the thermoplastic resins, the proportion of the thiourethane may be varied. In general, the blend may contain from 2% to 25% by weight of the cellulose ester thiourethane based on the combined weights of the cellulose ester thiourethane and the other plastic material or materials, such as the cellulose organic ester or thermoplastic resin.

Various changes and modifications may be made in practicing the invention without departing from the spirit and scope thereof and, therefore, the invention is not to be limited except as defined in the appended claims.

I claim:

1. A composition of matter comprising (1) a thiourethane of cellulose acetate, the thiourethane being selected from the group consisting of thiourethane, phenylthiourethane, ethylthiourethane, amylthiourethane, mono-benzyl thiourethane, dibenzyl thiourethane, allylthiourethane, methallylthiourethane, cyclohexylthiourethane, dibutylthiourethane, dimethylthiourethane and pyridylthiourethane and (2) a plastic material selected from the group consisting of polymethylene terephthalates and polymers of mono-ethylenically unsaturated monomers.

2. A composition as defined in claim 1 in which the thiourethane is present in the amount of 2 to 25% by Weight.

3. Composition of claim 1 in a solvent therefor.

4. A composition as defined in claim 3 in which the solvent is acetone.

5. A composition as defined in claim 3 in which the solvent is dimethylformamide.

6. A composition as defined in claim 3 in which the solvent is dimethylacetamide.

7. A composition as defined in claim 1 in which the plastic material comprises an initially thermoplastic synthetic resin.

8. A composition as defined in claim 1 in which the plastic material comprises a vinyl resin. N

9. A :omposition as defined in claim 1 in which the plastic material comprises an acrylonitrile polymer.

10. A composition as defined in claim 1 in which the plastic material comprises a copolymer of acrylonitrile containing at least by weight of acrylonitrile.

11. A composition as defined in claim 1 in which the plastic material comprises a copolymer of acrylonitrile containing at least 80% by weight of acrylonitrile.-

12. A composition as defined in claim 1 in which the plastic material comprises a copolymer of acrylonitrile containing 85 to 99% acrylonitrile and l to 15% of at least one other monoethylenically unsaturated monomer.

13. A composition as defined in claim 1 in which the plastic material comprises a polystyrene.

10 14. A composition as defined in claim 1 in which the plastic material comprises a copolymer of acrylonitrile and vinyl acetate.

15. A composition as defined in claim 1 in which the 5 plastic material comprises a copolymer of 97% acrylonitrile and 3% vinyl acetate.

No references cited. 

1. A COMPOSITION OF MATTER COMPRISING (1) A THIOURETHANE OF CELLULOSE ACETATE, THE THIOURETHANE BEING SELECTED FROM THE GROUP CONSISTING OF THIOURETHANE, PHENYLTHIOURETHANE, ETHYLTHIOURETHANE, AMYLTHIOURETHANE, MONO-BENZYL THIOURETHANE, DIBENZYL THIOURETHANE, ALLYLTHIOURETHANE, METHALLYLTHIOURETHANE, CYCLOHEXYLTHIOURETHANE, DIBUTYLTHIOURETHANE, DIMETHYLTHIOURETHANE AND PYRIDYLTHIOURETHANE AND (2) A PLASTIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF POLYMETHYLENE TEREPHTHALATES AND POLYMERS OF MONO-ETHYLENICALLY UNSATURATED MONOMERS. 